REINVESTIGATION OF EPOXIDATION USING TUNGSTEN-BASED PRECURSORS AND HYDROGEN-PEROXIDE IN A BIPHASE MEDIUM

被引:286
作者
AUBRY, C
CHOTTARD, G
PLATZER, N
BREGEAULT, JM
THOUVENOT, R
CHAUVEAU, F
HUET, C
LEDON, H
机构
[1] UNIV PIERRE MARIE CURIE, ITODYS, URA 34, F-75230 PARIS, FRANCE
[2] UNIV PARIS 07, F-75221 PARIS 05, FRANCE
[3] LAIR LIQUIDE, F-75321 PARIS, FRANCE
关键词
D O I
10.1021/ic00023a024
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of hydrogen peroxide with tungstic acid, "H2WO4", and various types of polyoxometalates (isopolyanions, [MnOy]x-, and heteropolyanions, [XM12O40]x'- and [X2M18O62]x"-, where M = Mo and W and X = P, B, and Si) has been studied by several physicochemical techniques (UV, IR, Raman, and P-31 and W-183 NMR spectroscopy). On the basis of these results, an interpretation of the differences in the catalytic activity of these precursors in the epoxidation of 1-octene by H2O2 in a biphase medium is proposed. Heteropolyacids (HPA) with the Keggin structure, H3[PM12O40] (M = Mo, W), are degraded in the presence of excess H2O2 to form peroxo species {PO4[M(O)(O2)2]4}3- and [M2O3(O2)4(H2O)2]2-. These anions were isolated in the form of salts and identified by elemental and spectroscopic analyses; it appears that the former is responsible for the catalytic activity of phase-transfer systems involving H3[PM12O40] as a precursor.
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页码:4409 / 4415
页数:7
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